S-(dithiophosphatyl) epoxyalkanes



United States Patent 3,349,103 S-(DITHEQPHOSPHATYIJEPGXYALKANES Henryl; A. Cyba, Evauston, Ill., assignor to Universal Oil Products Company, Des Plaines, 111., a corporation of Deiaware No Drawing. Filed Dec. 20, 1963, Ser. No. 332,304 Claims. (Cl. 260-648) This application is a continuation-in-part of my copending application Ser. No. 174,710 filed Feb. 21, 1962, now abandoned, which, in turn, is a continuation-in-part of application Ser. No. 836,084 filed Aug. 26, 1959, both said earlier applications being now abandoned, and relates to a novel composition of mattter.

The novel composition of matter is a dithiophosphatyl epoxyalkane and is represented by the following general formula:

Where R is a hydrogen or a hydrocarbon group, R is an alkylene group and R is selected from the group consisting of hydrogen, hydrocarbon and dithiophosphatyl.

In a preferred embodiment of the invention, R is an alkyl group of from 1 to 20 carbon atoms, R is an alkylene group of from 1 to 6 carbon atoms and R" is selected from the group consisting of hydrogen, an alkyl group of from 1 to 6 carbon atoms and a dithiophosphatyl group. The epoxyalkane moiety is the sum of the carbon atoms in R and R and accordingly is from 3 to 14 carbon atoms. These compounds are named as dialkyl dithiophosphatyl epoxyalkanes.

The novel compounds of the present invention are readily prepared by the reaction of an alkali metal dithiophosphate and a haloepoxide in the presence of an oxygen-containing polar solvent. It is essential that the reaction be elfected in the presence of the oxygen-containing polar solvent in order to form the novel compounds of the present invention by the interaction of the alkali metal component of the dithiophosphate and the halogen of the haloepoxide. When using a non-polar solvent, entirely different reaction products are obtained, apparently constituting an addition type reaction in which both the alkali metal and the halogen are retained in the final product. In addition to the difierence in chemical composition of the different products, those prepared in accordance with the present invention are distillable, whereas those prepared in the presence of a non-polar solvent are not distillable.

For economic reasons, sodium or potassium is preferred as the alkali metal component, although it is understood that lithium, rubidium or cesium may be utilized in some cases. The reaction is readily effected by refluxing the alkali metal salt of the dithiophosphate and the haloepoX- ide in the presence of the oxygen-containing polar solvent.

In a preferred embodiment, epichlorohydrin is used as the haloepoxide and the resultant compounds will c0mprise those in which R in the above general formula is a methylene radical and R" is hydrogen. When reacted with sodium or potassium dithiophosphoric acid, R in the above general formula is hydrogen and the resultant compound is l-S-dithiophosphatyl 2,3-epoxypropane. In a preferred embodiment, the dithiophosphatyl component preferably contains 1 or 2 alkyl groups, each containing from about 1 to about 20 carbon atoms. Illustrative compounds formed by the reaction of epichlorohydrin with such dialkyldithiophosphates include 1-S-(0,0-dimethyl dithiophosphatyl) 2,3-epoxypropane, 1-S-(0,0-diethyl dithiophosphatyl) 2,3-epoxypropane, and when used in luice bricating oils, higher alkyl derivatives are preferred, such (0,0-dipropyl dithiophosphatyl) 2,3-epoxypropane, (0,0-dibutyl dithiophosphatyl) 2,3-epoxypropane, (0,0 iiamyl dithiophosphatyl) 2,3-epoxypropane, (0,0-dihexyl dithiophosphatyl) 2,3-epoxypropane, (0,0-diheptyl dithiophosphatyl) 2,3-epoxypropane, (0,0-dioctyl dithiophosphatyl) 2,3-epoxypropane, (0,0-dinonyl dithiophosphatyl) 2,3-epoxypropane, (0,0-didecyl dithiophosphatyl) 2,3-epoxypropane, (0,0-diundecyl dithiophosphatyl) 2,3-epoxypropane, (O(O-didodecyl dithiophasphatyl) 2,3-epoxypropane, -(0,0-ditridecyl dithiophosphatyl) 2,3-epoxypropane,"

l-s i g O-dipentadecyl dithiophosphatyl) 2,3-ep0xyprol-si g O-dihexadecyl dithiophosphatyl) 2,3-epoxyprol-S i gb-diheptadecyl dithiophosphatyl) 2,3-epoxyprol-S i oib-dioctadecyl dithiophosphatyl) 2,3-epoxyproli i o-dinonadecyl dithiophosphatyl) 2,3-epoxyprol- -g oi o-dieicosyl dithiophosphatyl) 2,3-epoxypropane,

Generally the alkyl groups are the same as illustrated in the compounds specifically set forth above. In some cases the alkyl groups may be different as, for example, in compounds as l-S-(O-propyl-O-amyl dithiophosphatyl) 2,3-epoxypropane, 1 S (O-amyl-O-tridecyl dithiophosphatyl) 2,3-epoxypropane, etc.

Illustrative compounds in which a monoalkyl dithio phosphate is reacted with epichlorohydrin include l-S-(O- propyl dithiophosphatyl) 2,3-epoxypropane, l-S-(O-butyl dithiophosphatyl) 2,3-epoxypropane, l-S-(O-amyl dithiophosphatyl) 2,3-epoxypropane, l-S-(O-hexyl dithiophosphatyl) 2,3 epoxypropane, l S (O-heptyl dithiophosphatyl) 2,3-epoxypropane, l-S-(O-octyl dithiophosphatyl) 2,3-epoxypropane, l-S-(O-nonyl dithiophosphatyl) 2,3- epoxypropane, l-S-(O-decyl dithiophosphatyl) 2,3-epoxypropane, l-S-(O-undecyl dithiophosphatyl) 2,3-epoxypropane, l-S-(O-dodecyl dithiophosphatyl) 2,3-epoxypropane, l-S-(O-tridecyl dithiophosphatyl) 2,3-epoxypropane, l-S- (O-tetradecyl dithiophosphatyl) 2,3-epoxypropane, etc. The alkyl group or groups may be straight or branched chain. It is understood that mixtures of the monoand dialkyl substituted compounds may be employed. In some cases, mixtures of the monoand dialkyl dithiophosphates are available commercially, generally at a lower price, and such mixtures conveniently are used in preparing the novel compounds of the present invention.

Where R in the above general formula is a dithiophosphatyl group, the compounds are produced by the reaction of a dihaloepoxide and alkali metal dithiophosphate. Illustrative compounds formed by the reaction of 1,4-dichloro2,3-epoxybutane with dialkyl dithiophosphates are 1,4-bis-S-(0,0-dipropyl dithiophosphatyl) 2,3-epoxybutane,

l,4-bis-S-(0,0-dibutyl dithiophosphatyl) 2,3-epoxybutane,

1,4-bis-S-(0,0-diamyl dithiophosphatyl) 2,3-epoxybutane,

1,4-bis-S-(0,0-dihexyl dithiophosphatyl) 2,3-epoxybutane,

1,4-bis-S-(0,0-diheptyl dithiophosphatyl) 2,3-epoxybutane,

1,4-bis-S-(0,0-dioctyl dithiophosphatyl) 2,3epoxybutane,

1,4-bis-S-(0,0-dinonyl dithiophosphatyl) 2,3-epoxybutane,

l,4-bis-S-(0,0-didecyl dithiophosphatyl) 2,3-epoxybutane,

3 1,4-bis-S-(0,0-diundecyl dithiophosphatyl) 2,3-epoxybutane, l,4-bis-S-(0,0-didodecyl dithiophosphatyl) 2,3-epoxybutane, 1,4-bis-S-(0,0-ditridecyl dithiophosphatyl) 2,3-epoxybutane, 1,4-bis-S-(0,0-ditetradecyl dithiophosphatyl) 2,3-epoxybutane, l,4-bis-S-(0,0-dipentadecyl dithiophosphatyl) 2,3-epoxybutane, 1,4-bis-S-(0,0-dihexadecyl dithiophosphatyl) 2,3-epoxybutane, 1,4-bis-S-(0,0-diheptadecyl dithiophosphatyl) 2,3-epoxybutane, 1,4-bis-S-(0,0-dioctadecyl dithiophosphatyl) 2,3-epoxybutane, 1,4-bis-S-(0,0-dinonadecyl dithiophosphatyl) 2,3-epoxybutane, 1,4bis-S-(0,0-dieicosyl dithiophosphatyl) 2,3-epoxybutane, etc.

Here again, monoalkyl dithiophosphates or mixtures of the monoand dialkyl dithiophosphates may be employed for reacting with l,4-dichloro-2,3-epoxybutane. Also, the alkyl group or groups may be straight or branched chain.

It is understood that any suitable haloepoxy compound may be used for reacting with the alkali metal dithiophosphate. In general, the haloepoxy compound will contain from 3 to 6 or more carbon atoms. Illustrative chloro substituted epoxides include epichlorohydrin, 1,2-epi@4- chlorobutane, 2,3-epi-4-chlorobutane, 1,2-epi-5-chloropentane, 2,3-epi-5-chloropentane, 1,2-epi-6-chlorohexane, 2,3- epi-6-chlorohexane, etc. Dichloro substituted epoxides include 1,4 dichloro 2,3 epoxybutane, 1,5-dichloro-2,3- epoxypentane, 1,6-dichloro-2,3-epoxyhexane, 1,6-dichloro- 3,4-epoxyl1exane, etc. The chloro substituted compounds generally are preferred, although the bromo substituted compounds may be used. In still other cases, the corresponding iodo or fluoro substituted compounds may be employed.

As hereinbefore set forth, the preferred compounds comprise those in which R in the above general formula is an alkyl group and, in one embodiment, R also is an alkyl group. In another embodiment R and/or R may be selected from other hydrocarbon groups including alkylene, aryl, alkaryl, aralkyl, cycloalkyl, etc. These other hydrocarbon groups preferably contain from 1 to about 20 carbon atoms for the aliphatic groups and from 6 to about 20 carbon atoms for the aryl groups. Illustrative examples of such compounds include l-S-(Oheptadecenyl dithiophosphatyl) 2,3-epoxypropane,

1-S-(0,0-dipentenyl dithiophosphatyl) 2,3-epoxypropane,

1,4-bis-S-(O-pentadecenyl dithiophosphatyl) 2,3-epoxybutane,

1,4-bis-S-(0,0-diheptenyl dithiophosphatyl) 2,3-epoxybutane, etc.,

I-S-(O-phenyl dithiophosphatyl) 2,3-epoxybutane,

1-S-(0,0-diphenyl dithiophosphatyl) 2,3-epoxypropane,

1,4-bis-S-(O-phenyl dithiophosphatyl) 2,3-epoxybutane,

1,4-bis-S-(0,0-diphenyl dithiophosphatyl) 2,3-epoxybutane, etc.,

1-S-(O-xylyl dithiophosphatyl) 2,3-epoxypropane,

1-S-(0,0-ditolyl dithiophosphatyl) 2,3-epoxypropane,

1,4-bis-S-(O-propylphenyl dithiophosphatyl) 2,3-epoxybutane,

1,4-bis-S-(0,0-dixylyl dithiophosphatyl) 2,3-epoxybutane,

1,4-bis-S-(O-ethylphenyl dithiophosphatyl) 2,3-epoxybutane,

1,4-bis-S-(0,0-ditolyl dithiophosphatyl) 2,3-epoxybutane, etc.,

l-S-(O-phenbutyl dithiophosphatyl) 2,3-epoxypropane,

1-S-(0,0-diphenethyl dithiophosphatyl) 2,3-epoxypropane,

It is understood that the various compounds which may be prepared in accordance with the present invention are not necessarily equivalent in the utility thereof in a particular application.

As hereinbefore set forth, the novel compounds of the present invention are readily prepared by the reaction of an alkali metal dithiophosphate and a haloepoxide in the presence of the oxygen-containing polar solvent. When R" in the above general formula is a hydrocarbon group, the phosphate and haloepoxide are reacted in equal mole proportions. When R in the above general formula is a dithiophosphatyl group, 2 mole proportions of the dithiophosphate are reacted with 1 mole proportion of the haloepoxide. The reaction is readily effected by refluxing the reactants for a time suflicient to accomplish the desired reaction. This may range from 0.5 to 48 hours or more and generally will be for a time of from about 3 to about 20 hours. The refluxing temperature generally will be within the range of from about 30 to about 150 C. and preferably about 50 to about C. The pressure may range from atmospheric to 1000 p.s.i.g. or more.

As hereinbefore set forth, it is assential that the reaction is effected in the presence of an oxygen-containing polar solvent. Any suitable oxygen-containing polar solvent is employed including alcohols, particularly methanol, ethanol, propanol, butanol, etc., ketones including acetone, methyl ethyl ketone, diethyl ketone, dipropyl ketone, etc., glycols, glycol ethers, alkylamides, dimethylformamide, dimethylacetamide, nitromethane, dimethyl or diethyl sulfoxide, dimethyl ether, diethyl ether, etc. When desired, either or both of the reactants may be prepared as a solution in the solvent for ease of handling or in forming a more fluid mixture, or the solvent may be added to the reaction mixture. The solvent permits effecting the reaction at lower temperature and thereby favors the formation of monomers. Polymers are formed at the higher temperatures. The polymers or polycondensates are not harmful in lubricating oils, but are undesirable in pesticidal and insecticidal formulations.

In one method of operation the haloepoxide and alkali metal dialkyl dithiophosphate are formed as separate solutions in an alcoholic solvent. The solutions then are mixed, and the mixture is heated and maintained at refluxing conditions for the desired time. Following the completion of the reaction, the desired product is recovered in any suitable manner. The reaction mixture is filtered to remove the alkali metal salt formed in the reaction, after which the product may be dissolved in an aromatic solvent, washed with water and/or sodium bicarbonate or similar solution, dried over anhydrous sodium sulfate, anhydrous potassium carbonate or the like, and then filtered and heated to remove the aromatic solvent, the latter generally being etfected under vacuum. It is understood that the product may comprise a mixture of compounds but will include the desired product herein described. In most cases the product comprising a mixture of compounds may be used as such. However, when desired, the product may be further treated to separate specific compounds.

The compositions of this invention possess insecticidal properties with good inner-therapeutic action. They may be employed against many types of mites and insects such as, for example, Corausius larvae, Cotoneaster aphid,

apple aphid, black bean aphid, aster aphid, green peach aphid, chrysanthemum aphid, pea aphid, etc. The compounds or mixture of these may be used for the control of various larvae, mites, eggs of mites and such insects as flour beetle, Mexican bean beetle, black carpet beetle, milkweed bug, German cockroaches, southern armyworms, mealy bug, sow bug, citrus red spider, greenhouse red spider, various mosquitoes, yellow fever mosquito, malarial mosquito, etc.

The novel composition of matter of the present invention is particularly useful as an additive to hydrocarbon oil and still more particularly to lubricating oil. In the latter oil, the compound serves a number of important functions such as oxidation inhibitor (peroxide decomposer), bearing corrosion inhibitor, ring antiplugging additive, extreme pressure additive, detergent, etc.

The lubricating oil may be straight mineral lubricating oil derived from paraiiinic, naphthenic, asphaltic or mixed base petroleum crudes or blends thereof and is generally highly refined. In another embodiment the lubricating oil is a synthetic lubricating oil and may be one or a mixture of various types including aliphatic esters, polyalkylene oxides, silicones, esters of phosphoric and silicic acids, highly fluorine-substituted hydrocarbons, etc. Of the aliphatic esters, di-(Z-ethylhexyl) sebacate is being used on a comparatively large commercial scale. Other aliphatic esters include dialkyl azelates, dialkyl suberates, dialkyl pimelates, dialkyl adipates, dialkyl glutarates, etc. Specific examples of these esters include dihexyl azelate, di-(Z-ethylhexyl) azelate, di-3,5,5-trimethylhexyl glutarate, di-3,5,5-trimethylpentyl glutarate, di-(Z-ethylhexyl) pimelate, di-(Z-ethylhexyl) adip ate, triamyl tricarballylate, pentaerythritol tetracaproate, dipropylene glycol dipelargonate, 1,5-pentanediol-di-(Z-ethylhexanonate), etc. The polyalkylene oxides and derivatives include polyisopropylene oxide, polyisopropylene oxide diether, polyisopropylene oxide diester, etc. The silicones include methyl silicone, methylphenyl silicone, etc., and the silicates include, for example, tetraisooctyl silicate, etc. Synthetic lubricants proposed for use in high temperature service as, for example, jet fuel lubrication are pentaerythritcl esters and trimethylol propane esters.

The novel composition of the present invention also is useful as an additive to lubricating greases. These may be either of synthetic or petroleum origin. The synthetic greases generally are referred to as lithium base grease, sodium base grease, calcium base grease, barium base grease, strontium base grease, aluminum base grease, etc. These greases are solid or semi-solid gels and, in general, are prepared by the addition to mineral or synthetic lubricating oils of hydrocarbon-soluble metal soaps or salts of higher fatty acids as, for example, lithium stearate, calcium stearate, aluminum naphthenate, etc. The grease may contain thickening agents such as silica, carbon black, polyacrylates, talc, etc. Another type of grease is prepared from oxidized petroleum wax, to which the saponifiable base is combined with the proper amount of the desired saponifying agent, and the resultant mixture processed to produce a grease. Other types of greases in which the features of the present invention are usable include petroleum grease, whale grease, wool grease, etc., and those made from inedible fats, tallow, butchers waste, etc.

The novel composition also is useful in the stabilization of polyolefins and particularly polyethylene. The polyolefins preferably are of high molecular weight, usually having a molecular weight above 1000 and extending into the hundreds of thousand range. Generally, these are synthetically prepared. A typical example is the widely used polyethylene plastics. Other polyolefins include polypropene, polybutene, mixed polymers of ethylene and propylene, ethylene and butene, propylene and butene, etc., as well as polymers of higher molecular weight olefins. These may be of the high density, medium density, or low density type. Polyethylene is utilized, for example, as thermoplastic molding or coating agent. Because of its high dielectric strength and its resistance to water, polyethylene is particularly advantageous for use as insulators or dielectrics in condensers and other similar electronic equipment. However, polyethylene is subject to attack by atmospheric oxygen, particularly at elevated temperatures, either in use or during manufacture, and this impairs the desirable properties thereof including, for example, a reduction in the desirable electric properties, gelation upon oxidation, etc.

Other organic substances which deteriorate in storage, during treatment and/or in use include hydrocarbons and particularly motor fuels such as unsaturated gasoline, blends of unsaturated and saturated gasolines, etc., as well as jet fuel, diesel oil, mineral oil, fuel oil, residual oil, drying oil, waxes, resins, rubber, etc. These substances are adversely affected by oxygen, with the resultant for- 'mation of one or more of undesirable gum, sediment,

discoloration, cracking, corrosion and/ or other deleterious reactions.

When used as an additive to organic substrates, the novel compounds of the present invention will be utilized in a concentration of from about 0.0001% to about 2 5% by weight of the organic substrate, although in some cases higher or lower concentrations may be employed. The exact concentration to be used will depend upon the particular substrate to be treated. In most cases concentrations from about 0.01% to about 2% by weight generally will be employed.

It is understood that the composition of the present invention may be used along with other additives incorporated in the organic substrate. For example, one or more of an additional additive, including metal deactivator, dye, viscosity index improver, pour point depressant, anti-foaming additive, lubricity and extreme pressure additive, anti-scufling additive, detergent, dispersant, corrosion inhibitor, etc., may be incorporated in the substrate. When desired, the composition of the present invention may be prepared as a mixture with one or more of these other additives and marketed and/ or incorporated in the substrate in this manner. The composition of the present invention may be incorporated in the organic substrate in any suitable manner and at any suitable stage of preparation. When incorporated in a liquid substrate, the composition of matter is added thereto and intimately mixed by conventional means. When added to a solid or semi-solid substrate, the composition of the present invention preferably is added during the manufacture thereof in order to obtain intimate mixing. For example, in the manufacture of grease, the composition of the present invention may be added to one or more of the components of the grease prior to compositing and processing thereof, or it may be added to the mix at any time, preferably before final processing in order to obtain intimate mixing and dissolving thereof in the grease. In other cases, a solid substrate may be dipped, soaked or immersed in the additive, or the latter may be sprayed, brushed or otherwise applied to the solid substrate.

The following examples are introduced to illustrate further the novelty and utility of the present invention but not with the intention of unduly limiting the same.

Example I 1-S-(0,0-diisopropyl dithiophosphatyl) 2,3-epoxypropane was prepared as follows: 126 g. of potassium diisopropyl dithiophosphate were dissolved in 200 g. of Formula 30 alcohol ethanol-10%methanol). The solution was heated to refluxing temperature and 50.6 g. of epichlorohydrin were added dropwise while mixing and refluxing for 14 hours. The product then was filtered to remove white crystalline potassium chloride, dissolved in benzene, washed with water, sodium bicarbonate solution, again with water, and finally dried over anhydrous potassium carbonate. The benzene was evaporated by heating on a steam bath under water pump vacuum. The product (1 S (0,0 diisopropyl dithiophosphatyl) 2,3-

epoxypropane) was recovered in a yield of 103 g. as a fluid light amber liquid, having a refractive index u of 1.5180.

Example 11 1,4 bis S (0,0 diisopropyl dithiophosphatyl) 2,3- epoxybutane was prepared as follows: 138 g. (0.5 mole-[-12 g.) of potassium diisopropyl dithiophosphate were dissolved in 200 g. of refluxing methanol. 35.25 g. (0.25 moles) of 1,4-dichloro-2,3-epoxybutane were dissolved in 20 g. of methanol and the resultant solution was added dropwise to the refluxing solution of potassium diisopropyl dithiophosphate. Refluxing was continued for 6 hours, after which the reaction mixture was allowed to cool, filtered to remove potassium chloride, toluene solvent added and then washed 3 times with water, dried over anhydrous sodium sulfate, filtered, and the toluene removed by heating on a steam bath under water pump vacuum. The product comprising 1,4-bis-S-(0,0-diisopropyl dithiophosphatyl) 2,3-epoxybutane was recovered in a yield of 87 g. as a reddish brown oily liquid, having an index of refraction 12 of 1.5278.

Example III The compounds prepared in Examples I and II were evaluated as additives to lubricating oil. These evaluations were conducted in a Lauson engine. In this series of tests, the runs were continued for 115 hours, using a jacket temperature of 210 F. and an oil temperature of 280 F. A typical commercial paraflinic-solvent extracted lubricating oil was used. Pertinent results of these runs are reported in the following table:

TABLE I Run Number Additive 0.5% by 0.5% by None weight of weight of Example I Example II product product Bearing wt. loss, gms 2. 9021 0.0027 0. 0049 Oil ring plugging, percent 5 0 0 Oil consumption, ml./hr 6.03 5. 23 10. 49 Used Oil:

Neutralization No 10. 78 0.87 0.68 Saponification No., mg.

KOH/gm 25. 9 2. 21 3. 51 Pentane insolubles, percent 5. 16 0. 90 0.51 Viscosity. SSU at From the data in the above table, it will be noted that the novel compounds of the present invention were very effective in reducing corrosion, as evidenced by the very low bearing weight loss as compared to Run No. 1 made in the absence of the additive. Also, the compounds were eifective in preventing undesired changes in the lubricating oil, as evidenced by the neutralization number, saponification number, percent pentane insolubles and viscosities.

Example IV 1-S-(0,0 *ditridecyl dithiophosphatyl) 2,3-epoxypropane was prepared as follows: 165 g. of ditridecyl dithiophosphate were reacted with 19.5 g. of potassium hydroxide dissolved in 200 g. of Formula 30 alcohol, following which 30 g. of epichlorohydrin were added dropwise, while refluxing for 13 hours. The reaction mixture was cooled, filtered to remove potassium chloride, dissolved in benzene, washed twice with Water, dried over anhydrous sodium sulfate, filtered and the benzene removed by distilling on a steam bath under vacuum. The product [1-S-(0,0-ditridecyl dithiophosphatyl) 2,3-epoxypropane] was recovered in a yield of greater than 170 g. as an 3 amber colored liquid, having an index of refraction 11 of 1.4885.

Example V Example VI l,4-bis-S-(0,0-ditolyl dithiophosphatyl) 2,3-epoxybutane is prepared by reacting 2 molar proportions of ditolyl dithiophosphate potassium chloride with 1 molar proportion of 1,4-dibrorno-2,3-epoxybutane. The reaction is effected in substantially the same manner as hereinbefore set forth and the desired product is recovered by washing, filtering to remove potassium chloride and vacuum distillation to remove entrained solvent.

Example VII 1,4-bis-S-(0,0 dicyclohexyl dithiophosphatyl) 2,3-epoxypentane is prepared by reacting 2 molar proportions of dicyclohexyl dithiophosphate sodium salt with 1 molar proportion of 1,5-dichloro-2,3-epoxypentane. The reaction is eifected in substantially the same manner as hereinbefore set forth and the desired product is recovered by washing, filtering to remove sodium chloride and distilling under vacuum to remove entrained solvent.

Example VIII 1-S-(O-stearyl-O-2-ethylbutyl dithiophosphatyl) 2,3-epoxypropane was prepared by reacting 114.6 g. of O-stearyl-O-2-ethylbutyl dithiophosphoric acid with 8 g. of sodium hydroxide to form the sodium salt and then reacting the sodium salt with 18.5 g. of epichlorohydrin in the presence of 200 g. of methanol. The reaction mixture was refluxed for 3 hours. Sodium chloride was filtered off and the product worked up in the manner hereinbefore described.

When evaluated in the Lauson engine as described in Example III, the oil containing one-half percent by weight of the above additive resulted in a bearing weight loss of 0.0625, 0% oil ring plugging and oil consumption of 5.97 mL/hrs. All parts were free.

Example IX l-S (0,0-diethyl dithiophosphatyl) 2,3-epoxypropane is prepared as follows: 98 g. of potassium diethyl dithiophosphate are dissolved in 200 g. of methanol. The solution is heated to refluxing temperature and 25 g. of epichlorohydrin are added dropwise while mixing and refluxing for 10 hours. The product then is filtered to remove crystalline potassium chloride, dissolved in benzene, washed with water, dried over anhydrous sodium nitrate, and the benzene is evaporated on a steam bath under water pump vacuum. The product is recovered as a fluid light amber liquid.

Example X 1,4-bisS-(0,0-diethyl dithiophosphatyl) 2,3-epoxybutane is prepared as follows: g. (0.5 mole+12 g.) of potassium diethyl dithiophosphate are dissolved in 200 g. of refluxing Formula 30 alcohol. 35.25 g. (0.25 mole) of 1,4-dichloro 2,3-epoxybutane are dissolved in 20' g. of Formula 30 alcohol and the resultant solution is added dropwise to the refluxing solution of potassium diethyl dithiophosphate. Refluxing is continued for 6 hours, after which the mixture is filtered to remove crystalline potassium chloride, toluene solvent is added and then washed 3 times with water, dried over anhydrous sodium sulfate and the toluene removed by heating on a steam bath under water pump vacuum. The product is recovered as a reddish brown oily liquid.

I claim as my invention:

1. An S-(dithiophosphatyl) epoxyalkane having the formula where R is selected from the group consisting of hydrogen and hydrocarbon of from 1 to 20 carbon atoms, R is alkylene of from 1 to 6' carbon atoms, R" is selected from the group consisting of hydrogen, alkyl of from 1 to 6 carbon atoms and dithiophosphatyl, and the sum of R and R equals from 3 to 14 carbon atoms.

2. 1 S (O alkyl dithiophosphatyl) 2,3 epoxyalkane wherein said alkyl contains from 1 to 20 carbon atoms and said epoxyalkane contains from 3 to 14 carbon atoms.

3. 1 S (O heptadecenyl dithiophosphatyl) 2,3- epoxypropane.

4. 1 S (0,0 dialkyl dithiophosphatyl) 2,3 epoxyalkane wherein the alkyls each contain from 1 to 20 carbon atoms and said apoxyalkane contains from 3 to 14 carbon atoms.

5. 1 S (0,0 diisopropyl dithiophosphatyl) 2,3- epoxypropane.

6. 1 S (0,0 diethyl dithiophosphatyl) 2,3 epoxypropane.

7. 1,4 bis S (O alkyl dithiophosphatyl) 2,3- epoxyalkane wherein said alk-yl contains from 1 to 20 carbon atoms and said epoxyalkane contains from 3 to 14 carbon atoms.

8. 1,4 bis S (0,0 dialkyl dithiophosphatyl) 2,3- epoxyalkane in which the alkyls each contain from 1 to 20 carbon atoms and said epoxyalkane contains from 3 to 14 carbon atoms.

9. 1,4 bis S (0,0 diisopropyl dithiophosphatyl) 2,3-epoxybutane.

10. 1,4 bis S (0,0 ditolyl dithiophosphatyl) 2,3- epoxybutane.

References Cited UNITED STATES PATENTS 2,181,085 11/1939 Alquist et al 260348 2,181,100 11/1939 Slagh et a1. 260348 2,221,771 11/1940 Alquist et a1 260348 2,252,039 8/1941 Schirm 260348 X 2,434,099 1/1948 Bousquet 260348 2,494,283 1/1950 Cassaday et al. 260461.112 2,494,284 1/1950 Cassaday et a1. 260461.112 3,004,996 10/1961 Arakelian et al. 260348 X 3,019,250 1/1962 Kayser 260-348 X WALTER A. MODANCE, Primary Examiner.

JOHN D. RANDOLPH, Examiner.

N. S. MILESTONE, Assistant Examiner. 

1. AN S-(DITHIOPHOSPHATYL) EPOXYALKANE HAVING THE FORMULA 